US4237213A - Image forming method - Google Patents

Image forming method Download PDF

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Publication number
US4237213A
US4237213A US05/948,238 US94823878A US4237213A US 4237213 A US4237213 A US 4237213A US 94823878 A US94823878 A US 94823878A US 4237213 A US4237213 A US 4237213A
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United States
Prior art keywords
image
heat
development
silver
photosensitive material
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US05/948,238
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English (en)
Inventor
Ichiro Endo
Hajime Kobayashi
Yasuhiro Yano
Takao Muramatsu
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Canon Inc
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Canon Inc
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Priority claimed from JP897876A external-priority patent/JPS5292722A/ja
Priority claimed from JP897976A external-priority patent/JPS5292723A/ja
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/263—Processes using silver-salt-containing photosensitive materials or agents therefor with an exterior influence, e.g. ultrasonics, electrical or thermal means
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49836—Additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S101/00—Printing
    • Y10S101/37—Printing employing electrostatic force
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/136—Coating process making radiation sensitive element

Definitions

  • This invention relates to an image forming method and a heat-development type photosensitive material to be used therefor. More particularly, the invention is concerned with the image forming method which uses the heat-development type photosensitive material containing therein an organic silver salt, and such heat-development type photosensitive material suited for the purpose.
  • Photosensitive materials containing therein silver halide have heretofore been used widely in forming a picture image.
  • these photosensitive materials are of wet type in their development and image fixation, there are various disadvantages still to be improved such that the treatment process is complicated and takes much time, that the treatment process must be conducted in a dark room, that undesirable effects are likely to be caused to human body working in such chemical treatment in the dark room, and others.
  • This image forming method is of such type that, when the abovementioned heat-development type photosensitive material is subjected to an image exposure, a very small amount of silver is isolated from the photosensitive silver halide in the catalytic quantity to form a latent image, and this small amount of isolated silver functions, during the subsequent heat-development process, as a nucleus for development of silver which is isolated from the organic silver salt and deposited with the aid of the reducing agent, thereby forming a visible picture image.
  • the image forming process is totally of the dry type, which process has drawn increasing concern from all fields. And, the improvement and development in the heat-development type photosensitive material used therefor are very active. At the same time, this image forming method has been attaining wider applications in various aspects such as use as an electrostatic printing master which is disclosed in U.S. Pat. No. 599,061 filed by the present applicants, and as recording material in many fields.
  • the heat-development type photosensitive material to be used for such image forming method has its advantage in that it is capable of carrying out the entire treatment process in the dry condition, it has various disadvantageous problems to occur at the time of the actual image formation owing to the entire substances required for the image formation being made coexistent from the initial stage of preparing the heat-development type photosensitive material. That is, there is a considerable lapse of time from preparation of the heat-development type photosensitive material to the actual image forming operation using the same.
  • each sheet to be completely sealed in an individual envelope as mentioned above, or that, in the case of such sheets being enveloped in bulk and the envelope being once opened for use of some of the sheets, the envelope be tightly sealed again immediately after the required number of sheets are taken out of the envelope, or that the sheets remaining unused in the open envelope be kept in a desired atmosphere to maintain their performance, and so forth.
  • the abovementioned points constitute extreme inconveniences. That is to say, the abovementioned electrostatic printing master is obtained by subjecting the heat-development type photosensitive material to an image exposure and heat-development treatments to form a silver image pattern therein, the electrostatic printing method of which is to subject the electrostatic printing master having such silver image pattern to electrostatic charging, development of an image, and transfer of the developed image.
  • the principle of the electrostatic printing is based on the fact that, at the time of the electrostatic charging step, the exposed portion (silver image portion) of the master is relatively electrically conductive and relatively small in its electrostatic charge sustaining capability, while the non-exposed portion (non-silver image portion) has such electrostatic charge sustaining capability, owing to which there occurs an electrostatic potential contrast. Therefore, deterioration in the image forming capability with lapse of time of the heat-development type photosensitive material as the forming material of the electrostatic printing master inevitably invites, for example, insufficiency of the silver deposition at the exposed portion of the photosensitive material to unfavorably cause the quality of the transferred image to lower due to decrease in the electrostatic potential contrast.
  • the present inventors conducted diligent researches and studies from various aspects on the heat-development type photosensitive material containing therein an organic silver salt, as the result of which they have found that inclusion of a development accelerator represented by a reducing agent from the initial stage of preparing the photosensitive material constitutes the very point of problem in the deterioration of the image forming quality of the material.
  • the state of coexistence of the organic silver salt and the development accelerator to impart a preferable performance of the photosensitive material at the initial stage of its preparation appears to change with lapse of time to cause the aforementioned problems to occur, or the development accelerator per se deteriorates with lapse of time due to, for example, its scattering outside of the system through evaporation, or both decomposition and evaporation.
  • the present invention has been made in view of the afore-described points of problem, and can solve all of them.
  • an image forming method which comprises adding a development accelerator (d) to a heat-development type photosensitive raw material containing therein at least an organic silver salt (a), a halide (b), and a binder (c) at the time of forming an image through the image exposure and heat-development steps.
  • a heat-development type photosensitive material in which the development accelerating property thereof is imparted thereto, or its development accelerating property is augmented by addition of a development accelerator (d) at the time of the image formation.
  • the present invention is capable of imparting to the photosensitive raw material containing therein an organic silver salt (a), a halide (b), and a binder (c) the development accelerating property, or such property almost comparable or even superior to that at the initial stage of preparing the heat-development type photosensitive material by adding a development accelerator (d) at the time of forming an image thereon through exposure and heat-development.
  • the development accelerator (d) to be used in the present invention is such one that functions to accelerate the developing action at the exposed portion of the heat-development type photosensitive material at the time of the image exposure and heat-development thereon.
  • the representative substance for this development accelerator is a reducing agent.
  • the development accelerator (d) a stabilizer to preserve a produced image in a stabilized condition, a sensitivity-increased coloring matter, and a color adjustor for controlling color tone of an image at the time of the image formation, and others.
  • the characteristic feature of the present invention resides in imparting to, or augmenting in, the abovementioned heat-development type photosensitive material the development accelerating property by adding the abovementioned development accelerator (d) when the photosensitive material is subjected to the image forming process. Accordingly, the image forming method according to the present invention may be adopted in either case where the development accelerator is contained at the time of preparing the heat-development type photosensitive material, or where no such development accelerator is contained therein.
  • the development accelerator in the heat-development type photosensitive material, therein the development accelerator is contained previously at the time of preparing the photosensitive material, the development accelerating property is augmented by fresh addition of such development accelerator at the time of the image formation, so that the effect of deterioration in the image forming capability of the heat-development type photosensitive material due to change, with lapse of time, in the development accelerator contained therein can be reduced to the minimum possible extent. Even in case the development accelerator is not changed so much with lapse of time, there can be accrued further improvement in the image forming capability owing to increase in the development accelerating property of the photosensitive material by addition of the development accelerator at the time of the image formation.
  • the development accelerator is to impart to the heat-development type photosensitive material the required development accelerating property at the time of its image formation, even when the photosensitive raw material does not include therein the development accelerator at the time of its preparation, no particular preventive measures need be taken against deterioration of the development accelerator during the storage period starting from its preparation to the image formation thereon, which is an advantage of the present invention.
  • the heat-development type photosensitive raw material according to the present invention may usually be obtained by mixing and dispersing an organic silver salt (a) and a halide (b) in a binder (c), and applying the dispersion onto an appropriate supporting body or a substrate to form the same into an organic silver salt layer.
  • organic silver salt for the organic silver salt to be used in such heat-development type photosensitive raw material, there can be enumerated silver salts of organic acids, mercapto compounds and imino compounds, and organic silver complex salts as shown in the following.
  • the silver salts of organic acids particularly, silver salts of fatty acids, are effective.
  • Silver salt of aliphatic dicarboxylic acid For example, silver oxalate.
  • Silver salt of oxycarboxylic acid For example, silver hydroxy-stearate.
  • silver benzoate for example, silver benzoate, silver 0-aminobenzoate, silver p-nitrobenzoate, silver phenylbenzoate, silver acetamidobenzoate, silver salicylate, silver picolinate, and silver 4-n-octadecyloxydiphenyl-4-carboxylate.
  • silver phthalate and silver quinolinate.
  • silver ⁇ , ⁇ '-dithiodipropionate, silver ⁇ , ⁇ '-dithiodipropionate and silver thiobenzoate For example, silver ⁇ , ⁇ '-dithiodipropionate, silver ⁇ , ⁇ '-dithiodipropionate and silver thiobenzoate.
  • silver p-toluenesulfonate silver dodecylbenzenesulfonate and silver taurinate.
  • silver diethyldithiocarbamate For example, silver diethyldithiocarbamate.
  • silver 2-mercaptobenzoxazole silver 2-mercaptobenzothiazole and silver 3-mercaptobenzimidazole.
  • silver 1,2,4-triazole, silver benzimidazole, silver benztriazole, silver 5-nitrobenzimidazole, silver 5-nitrobenztriazole and silver 0-sulfobenzimide For example, silver 1,2,4-triazole, silver benzimidazole, silver benztriazole, silver 5-nitrobenzimidazole, silver 5-nitrobenztriazole and silver 0-sulfobenzimide.
  • the inorganic halide is preferably that having the general formula: MXm wherein X represents a halogen (for example, Cl, Br, I), M represents hydrogen, ammonium or a metal (for example, potassium, sodium, lithium, calcium, strontium, cadmium, chromium, rubidium, copper, nickel, magnesium, zinc, lead, platinum, palladium, bismuth, thallium, ruthenium, gallium, indium, rhodium, beryllium, cobalt, mercury, barium, silver, cesium, lanthanum, iridium, aluminum and the like), and m is 1 when M is hydrogen or ammonium and represents the valency of a metal when M is the metal.
  • X represents a halogen (for example, Cl, Br, I)
  • M represents hydrogen, ammonium or a metal (for example, potassium, sodium, lithium, calcium, strontium, cadmium, chromium, rubidium, copper, nickel, magnesium,
  • silver chlorobromide, silver chlorobromoidide, silver bromoiodide, silver chloroiodide may be also preferably used.
  • halide (b) may be used either singly or in combination of more than two kinds of these compounds. Adding quantity of the halide (b) is limited to such an extent that, at the time of the exposure, the nucleus for the development in an amount which does not affect the heat-development is formed, in other words, the minimum required photosensitivity is provided.
  • the reason for the abovementioned limitation to the amount of halide to be added is that, when it is added in more amount than necessary, the photosensitivity becomes higher than required owing to the presence of silver halide in the heat-development type photosensitive raw material which is photosensitive, owing to which the photosensitive material is considerably sensitized even with a very slight amount of light, e.g., when the heat-development type photosensitive raw material is unexpectedly exposed to light at the time of its storage, it immediately discolors, even if the exposure is in a very brief instant and under a very slight amount of light, to cause the so-called ground fogging; while, when it is added in less amount than necessary, the nucleus for the development cannot be formed in a quantity sufficient to accomplish the heat-development in an efficient manner.
  • the adding quantity of the halide to be determined should usually be from 1 mol to 10 -6 mol with respect to 1 mol of organic silver salt, or preferably from 10 -1 mol to 10 -6 mol, or optimumly from 10 -1 to 10 -5 mol.
  • the suitable method for the purpose may be of any known technique of forming a thin film from a synthetic resin material.
  • Such known coating methods are the application by rotation, in which the substrate is immersed in an emulsion, the air-knife method, the wire-bar coating method, pouring and spreading coating method, and so forth. Thickness of the film may be optionally adjusted depending on the purpose.
  • the binding agent, or binder to cause the organic silver salt (a) to disperse therein so as to form the organic silver salt layer
  • those material which are excellent in the film-forming capability, and which does not soften beyond its permissible extent at the time of the heat-developement to invite lowering in the binding property thereof, should be used.
  • the heat-development is to be carried out by means of a heated roller, there is possibility such that the image quality is liable to be disturbed due to softening of the binder (c), avoidance of which is most important.
  • selection of the binder (c) having such function that does not suppress isolation of silver from the organic silver salt (a) proper, but assist isolation of silver from the organic silver salt (a) at the exposed portion of the photosensitive material is highly recommendable.
  • the following conditions should desirably be satisfied, in addition to the afore-described various conditions. That is, when the master is prepared from the heat-development type photosensitive material and then it is used as the electrostatic printing master, since the electrostatic printing method is relied on the electrostatic contrast between the non-exposed portion (non-silver image portion) and the exposed portion (silver-image portion) to be obtained by the electric charging of the master surface by the corona discharge, etc., it is all the more important that the electrostatic charge be retained as much as possible at the non-exposed portion, and that, on the contrary, the electrostatic charge be not retained as far as possible at the exposed portion. It is therefore necessary that the binder (c) possesses an electric resistivity of an extent more than that is capable of retaining the electric charge therein.
  • the electrostatic printing master may be essentially satisfactory, if it has the electrostatic charge sustaining power of a certain extent at the non-exposed portion, and the electrostatic contrast between the non-exposed portion and the exposed portion is suitable for the practical purpose.
  • the binder (c) for the heat-development type photosensitive material be chosen to enable an electrostatic printing master, whose resistivity at the non-exposed portion is higher by two places and above, or optimumly, higher by three places and above, than that at the exposed portion on the master, to be formed.
  • the resistivity of the binder (c) should usually be 10 10 ohm-cm and above, more preferably 10 11 ohm-cm and above, and, optimumly, 10 13 ohm-cm and above.
  • the binder (c) should desirably be of non-hygroscopic property.
  • the electrostatic printing master when utilized, for example, in a highly humid atmosphere, if it is lack in the non-hygroscopic property, the electric resistance at the non-exposed portion of the master becomes lowered on account of moisture-absorption of the master, which leads to lowering in the electrostatic contrast, and, in addition, causes the electrostatic charge to flow toward the surface of the master.
  • the binder (c) should be so determined that the degree of non-hygroscopicity may be selected in accordance with the atmosphere, in which the master is to be used, or with the area or region, where the master is to be used (whether the area is highly humid or not).
  • the equilibrated moisture content should preferably be 3.0% or below, and optimumly, 2.0% or below, with respect to the relative humidity of from 20 to 100%.
  • binders for use in the present invention are enumerated as follows.
  • polyvinyl butyral polyvinyl acetate cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, polyvinyl alcohol, ethyl cellulose, methyl cellulose, benzyl cellulose, polyvinyl acetal, cellulose propionate, cellulose acetate propionate, hydroxyethyl cellulose, ethylhydroxy cellulose, carboxymethyl cellulose, polyvinyl formal, polyvinylmethylether, styrene-butadiene copolymer and polymethyl methacrylate. If necessary, two or more of these compounds may be mixed for use.
  • the binder (c) having satisfactory insulating property be selected out of the above listed group.
  • polyvinyl butyral when employed as the binder (c), it should preferably possess a mean degree of polymerization of from 500 to 1,000, a degree of butyralation of 60 mol% and above, and a residual acetyl group of 3 mol% and below.
  • plasticizer may be added.
  • Typical plasticizers are dioctyl phthalate, tricresyl phosphate, diphenyl chloride, methylnaphthalene, p-terphenyl, and diphenyl.
  • the adding quantity of the binder (c) may be properly determined on the basis of various conditions desired. It usually ranges from 0.02 to 20 parts by weight, or more preferably, from 0.1 to 5 parts by weight, with respect to 1 part by weight of organic silver salt.
  • solvents for dispersing the organic silver salt in the binder (c) there may be mentioned methylene chloride, chloroform, dichloroethane, 1,1,2-trichloroethane, trichloroethylene, tetrachloroethane, carbon tetrachloride, 1,2-dichloropropane, 1,1,1-trichloroethane, tetrachloroethylene, ethyl acetate, butyl acetate, isoamyl acetate, cellosolve acetate, toluene, xylene, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, dimethylamide, N-methylpyrrolidone, alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol and the like, and water.
  • the base may be a metal plate such as aluminum, copper, zinc, silver and the like, a metal laminate paper, a paper treated to prevent permeation of a solvent, a paper treated with a conductive polymer, a synthetic resin film containing a surface active agent; and a glass, a paper, a synthetic resin sheet and a film such as cellulose acetate film, polyethyleneterephthalate film, polycarbonate film, polystyrene film and the like which have on the surface a vapor-deposited metal, metal oxide or metal halide.
  • insulating glass, paper, synthetic resin and the like may be used.
  • an appropriate flexible metal sheet, paper on other conductive materials which can be wound on a drum are preferable.
  • an electrically conductive layer When an electrically conductive layer is to be provided on the surface of a non-conductive substrate such as a synthetic resin film, paper, or others, it may be placed on either surface where the organic silver salt layer is present or the surface opposite thereto, depending on the purpose of use. In case, however, the electrically conductive layer directly contacts the organic silver salt layer, it is preferable that the forming material of the electrically conductive layer be so selected that it may not react with organic silver salt (a).
  • the material for such substrate may be any kind if it has an inherent surface resistivity smaller than that at the non-silver image portion, i.e., 10 9 ohm-cm and below, or more preferably 10 5 ohm-cm and below, when the material is formed into the electrostatic printing master, and has no tendency to react with organic silver salt (a).
  • the timing for adding the development accelerator (d) to the abovementioned heat-development type photosensitive material should preferably be as close to the timing for the heat-development as possible.
  • addition of the development accelerator during a period of from immediately prior to the image exposure operation to immediately prior to commencement of the heat-development, or the addition of the development accelerator simultaneously with the heat-development accrues more effective and favorable results.
  • the addition of the accelerator after the image exposure but before the heat-development is considered desirable.
  • the abovementioned development accelerator (d) to be added to the heat-development type photosensitive material it is dissolved into an appropriate solvent together with a binder, or without the binder to thereby make it into solution. Or, it may be dispersed in an appropriate solvent, e.g., "ISOPAR" (a group of high purity isoparaffinic material produced by Humble Oil & Refining Co., U.S.A.). Any other appropriate, known method of addition may be feasibly adopted.
  • ISOPAR a group of high purity isoparaffinic material produced by Humble Oil & Refining Co., U.S.A.
  • the so-called dipping method wherein the substrate is immersed in a solution containing the development accelerator (d); the rotary coating method; the air-knife coating method; wire-bar coating method, the pouring and spreading method; spray coating method, brush coating method, the doctor-blade coating method, and so forth.
  • the roller coating method, dipping method, spray coating method, rotary coating method, etc. may be preferably adopted.
  • the heat development process wherein a material in sheet form containing therein the development accelerator (d) is caused to contact the surface of the organic silver salt layer of the heat-development type photosensitive raw material, and then it is subjected to the heat-development, may be effectively adopted.
  • the sheet material needs be closely contacted on the organic silver salt layer surface prior to the image exposure, and should have light transmitting property to the exposure light.
  • the advantage in the so-called “dual sheet type” method resides in that the image quality as at the time of its formation can be maintained semi-permanently, because, when the sheet contains the reducing agent as the development accelerator (d), unused reducing agent can be removed by peeling the abovementioned sheet off the organic silver salt layer surface after the heat-development treatment, whereby the so-called fogging due to the residual reducing agent after the development can be prevented.
  • the accelerator is rendered an atomized state or a vaporized state, and is then applied to the photosensitive material.
  • development accelerator (d) for use in the present invention those which have so far been employed in the name of reducing agents, stabilizers, sensitivity-increased coloring matters, tone adjusters, and so forth, may be used. These development accelerators may be used in a mixture of two or more kinds within such an extent that the components in the mixture do not mutually affect unfavorably. It is of course permissible that any appropriate ones selected from these development accelerators are individually added to the photosensitive material in the order as desired.
  • the effective reducing agents for the purpose of the present invention are phenols, bisphenols, naphthols, di- or poly-hydroxybenzenes, and so forth.
  • aminophenol 2,6-di-t-butyl-p-cresol and p-methylaminophenol sulfate(metol).
  • hydroquinone for example, hydroquinone, methylhydroquinone, chlorohydroquinone, bromohydroquinone, pyrogallol and catechol.
  • bisnaphthol reducing agents represented by bis- ⁇ -naphthol such as, for example, 2,2'-dihydroxyl-1,1'-binaphthyl, and so on, as disclosed in Japanese laid-open patent applications No. 46-6074 and No. 47-33621, are effective for the purpose.
  • dihydroxybenzene compounds such as 2,4-dihydroxybenzaldehyde; 2,4-dihydroxybenzophenone; 2,4-dihydroxyacetophenone; 2',4'-dihydroxy-4-methylbenzophenone; 2,4-dihydroxypropiophenone; 2,4-dihydroxybutylphenone.
  • dihydroxybenzene compounds such as 2,4-dihydroxybenzaldehyde; 2,4-dihydroxybenzophenone; 2,4-dihydroxyacetophenone; 2',4'-dihydroxy-4-methylbenzophenone; 2,4-dihydroxypropiophenone; 2,4-dihydroxybutylphenone.
  • sulfonamide phenol reducing agents as disclosed in U.S. Pat. No. 3,801,321, for example, can be effectively used.
  • the effective reducing agent for the method which utilizes the dual sheet type photo-sensitive material, there can be further used as the effective reducing agent a substance which is vested with the required reducing property by light irradiation.
  • a substance which is vested with the required reducing property by light irradiation is disclosed in, for example, Japanese laid-open patent application No. 50-140113.
  • this substance is obtained by combination of quinones, azides, and hydrogen donors, and can first be vested with the reducing property by light irradiation, if such light that imparts to the abovementioned substance the required reducing property, for example, is used as the image exposure light, the reducing agent is present only on the surface of the exposure portion of the organic silver salt layer, on account of which no fogging occurs at the non-exposed portion at the time of the heat-development, hence the image of a satisfactory quality can be obtained.
  • Preferred development accelerators (d) for use in the present invention include the following:
  • dye sensitizers such as merocyanine dyes having a rhodanine, thiohydantoin, or 2-thio-2,4-oxazolidinedione nucleus disclosed in Japanese Patent Laid Open No. Sho 48-28221; benzophenones having a benzene ring containing hydroxy and/or alkoxy substituent disclosed in Japanese Patent Laid Open No. Sho 49-115540; phthalazinone or phthalazinone compounds disclosed in Japanese Patent Laid Open No. Sho 49-22928; and cyclohexyl substituted isocyanate derivatives of phthalazinone disclosed in Japanese Patent Laid Open No. Sho 49-102329.
  • development accelerators (d) are added to the heat-development type photosensitive material by the aforedescribed methods.
  • the solvent and binder, in which the development accelerators are dissolved and dispersed, may be properly selected from those as enumerated in the foregoing for use in the formation of the organic silver salt layer, depending on preference.
  • polyvinyl chloride polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polystyrene, polymethyl methacrylate, polyurethane rubber, xylene resin, benzyl cellulose, ethyl cellulose, cellulose acetate butyrate, cellulose acetate, polyvinylidene chloride, chlorinated polypropylene, polyvinyl pyrrolidone, cellulose propionate, polyvinyl formal, cellulose acetate phthalate, polycarbonate, cellulose acetate propionate, gelatine and derivatives thereof, acrylamide polymer, chlorinated rubber, isobutylene, butadienestyrene copolymer, polyvinyl alcohol and the like.
  • the solvent there can be chosen any arbitrary one from those to be used for dispersing the abovementioned organic silver salt (a) and the binder (c).
  • the thus prepared heat-development type photosensitive material was left in a dark place for 30 days. After this storage, the following composition (I) was coated on the photosensitive layer surface of the photosensitive material by the use of a roll-coater, and was immediately dried with hot blast air.
  • composition (I) consists of 1.5 g of 2,2'-methylene bis-(6-t-butyl-p-cresol), 10 g of cellulose acetate (10 wt% acetone solution), and 30 g of acetone.
  • this photosensitive material was subjected to image-exposure through a positive image by means of a tungsten lamp (2,500 lux) for 12 seconds, after which the heat-development was conducted by means of a roller type heat-development device at a temperature of 130° C. for 3 seconds to thereby obtain a visible, negative print image. This was designated as "specimen S-1".
  • the forming composition of the abovementioned heat-development type photosensitive raw material was coated on art paper and dried, after which the abovementioned composition (I) was immediately coated over this photosensitive layer surface by means of the roll-coater, and dried to thereby prepare the heat-development type photosensitive material. After this, the photosensitive material was left for 30 days in a dark place, whereby "specimen S-2" was prepared in the same manner as in the case of the specimen S-1.
  • the heat-development type photosensitive material and the image forming method in this embodiment is apparently superior in its image quality and its preservability.
  • the heat-development type photosensitive raw material was prepared in the same manner as in Example 1 above, after which it was left in a dark place for 30 days. Then, the following composition (II) was spray-coated on the photosensitive layer surface of the photosensitive raw material, and immediately dried with hot blast air.
  • composition (II) consists of: 1.5 g of 2,2'-methylene-bis-(6-t-butyl-p-cresol) and 30 g of acetone.
  • composition (II) was spray-coated on the photosensitive layer surface of the abovementioned heat-development photosensitive raw material immediately after its preparation, dried, and left for 30 days in a dark place. Thereafter, the exposure and development were conducted in the same manner as in Example B 1 above to thereby obtain a specimen S-4.
  • this solution was coated on art paper by the use of a coatig rod, and dried to thereby prepare the heat-development type photosensitive raw material.
  • the thus prepared heat-development type photosensitive raw material was left in a dark place for one week under conditions of a temperature of 50° C. and relative humidity (RH) of 80%.
  • the photosensitive material was subjected to the image exposure operation through a positive image by using a tungsten lamp (2,500 lux) for 2 to 3 seconds, after which the photosensitive material was immediately immersed in a solution of the following composition (III), pulled up from the solution, and dried with hot blast air. Subsequently, by using the roller type heat-development device, the heat-development was conducted for 2 seconds at 130° C. to obtain a visible, negative print image. This was made the specimen S-5.
  • a tungsten lamp 2,500 lux
  • composition (III) consists of: 1.5 g of 2,2'-methylene-bis-(6-t-butyl-p-cresol), 0.3 g of phthalazinone, 10 g of cellulose acetate (10 wt.% acetone solution), and 30 g of acetone.
  • the abovementioned forming composition for the heat-development type photosensitive raw material was coated on art paper, then dried, and immediately coated with the composition (III) to prepare the heat-development type photosensitive material. Thereafter, the photosensitive material was also left in a dark place for one week under conditions of 50° C. and a relative humidity (RH) of 80%. After this storage in the dark place, the photosensitive material was subjected to the exposure and heat-development under the same conditions as in the specimen S-5, thereby obtaining a visible image. This was made the specimen S-6.
  • Example 3 The same procedures were followed as in Example 3, with the exception that the same quantity of silver stearate was used in place of silver behenate in Example 3.
  • Example 2 The same procedures were followed as in Example 1, with the exception that the same quantity of silver laurate was used in place of silver behenate. As the result, a favorable result was obtained with the heat-development type photosensitive material using silver laurate.
  • the undermentioned forming composition for the heat-development type photosensitive raw material was applied on art paper using a coating rod, and dried to obtain the raw material for the heat-development type photosensitive material.
  • the forming composition for preparing the heat-development type photosensitive raw material consists of: 25 g of silver behenate, 120 g of toluene, 120 g of methyl ethyl ketone, 100 g of polyvinyl butyral (10 wt.% ethyl alcohol solution), 100 mg of mercury acetate, 150 mg of sodium bromide, 2.5 g of phthalazinone, and 60 mg of 3,3'-diethyl-2,2'-thiacarbocyanine iodide.
  • the composition (I) used in Example 1 was applied on a polyester film by the use of a coating rod and dried to obtain a coated sheet. Then, the surface of this polyester sheet coated with the composition (I) and the photosensitive surface of the photosensitive raw material which had been subjected to the compulsory test as mentioned above were sufficiently contacted each other. After this closure contact, an image exposure was conducted for three seconds by using a tungsten lamp (2,500 lux) from the side of the polyester film through a positive image. Then, while the photosensitive raw material and the abovementioned polyester sheet were being contacted each other, the heat-development was conducted for 2 seconds at 130° C. using a roller type heat development device to obtain a visible negative print image, which was made a specimen S-7.
  • the abovementioned forming composition for the heat-development type photosensitive raw material was applied on art paper, and dried. Immediately after this drying operation, a composition (I) was applied and dried, thereby preparing a comparative heat development type photosensitive material. Following this, the photosensitive material was subjected to the compulsory test in a dark place at 50° C. and under a relative humidity of 80%, after which a specimen S-8 was prepared in the same manner as in the case of preparing the abovementioned specimen S-7.
  • the raw material for the heat-development photosensitive material was prepared in the same way as in Example 6 above, and the photosensitive material was left for two weeks in a dark place under conditions of 50° C. and a relative humidity of 80%. Thereafter, the following treatments were effected.
  • the raw material for the heat-development type photosensitive material was prepared in exactly the same manner as in Example 6 above, with the exception that 160 mg of rubidium bromide was added in place of calcium bromide. Thereafter, this photosensitive raw material was left in a dark place for three months.
  • a heat-development type photosensitive raw material was prepared by overcoating the composition (II) of Example 3 on the surface of the heat-development type photosensitive raw material of this example.
  • This photosensitive material was left in a dark place for three months, after which a specimen S-13 was prepared from this photosensitive material in the same manner as in the preparation of the specimen S-12.
  • the undermentioned forming composition for the heat-development type photosensitive raw material was coated on art paper by the use of a coating rod, and dried to thereby obtain the heat-development type photosensitive raw material.
  • the forming composition for the heat-development type photosensitive raw material was composed of: 25 g of silver behenate, 120 g of toluene, 120 g of methyl ethyl ketone, 50 mg of 5-acetyl-4-methyl-3-(3-oxobutyl)thiazoline-2-thione, and 160 mg of rubidium bromide.
  • the undermentioned separate composition (IV) was further coated on the polyester film by the use of a coating rod, and dried to thereby prepare the film having a layer which contains therein a reducing agent.
  • Composition (IV) 1.5 g of 2,2'-methylene-bis(6-t-butyl-p-cresol), 10 g of cellulose acetate (10 wt.% acetone solution), 0.4 g of phthalazinone, 8 mg of 3,3'-diethyl-2,2'-thiacarbocyanine iodide, and 30 mg of acetone.
  • the abovementioned heat-development type photosensitive raw material was left in a dark place for five months. Thereafter, the photosensitive layer surface of this photosensitive raw material and the surface of the abovementioned polyester film where the composition (IV) had been coated were sufficiently contacted each other. Next, an image exposure was conducted on this photosensitive material for 3 seconds by the use of a tungsten lamp (2,500 lux) from the side of the film surface through a positive image, and, subsequently, the heat-development was carried out for two seconds at 130° C. using a roller type heating device, whereby a negative print image was obtained. This was made a specimen S-14.
  • composition (IV) was coated on the abovementioned photosensitive raw material, and dried to thereby obtain the heat-development type photosensitive material.
  • This photosensitive material was left in a dark place for five months, after which a specimen S-15 was prepared in the same manner as in the case of preparing the specimen S-14.
  • the heat-development type photosensitive raw material was prepared in exactly the same manner as in Example 9, with the exception that silver caproate was used in place of silver behenate in the same quantity.
  • the same measurements as in Example 9 above were made on this photosensitive raw material, and the same favorable results as those in Example 9 were obtained.
  • the heat-development type photosensitive raw material was prepared by applying the undermentioned forming composition for the heat-development type photosensitive raw material onto art paper by the use of a coating rod, and then drying the coating sufficiently.
  • the forming composition for the heat-development type photosensitive raw material was composed of 25 g of silver behenate, 120 g of toluene, 120 g of methyl ethyl ketone, 120 mg of mercury acetate, 50 mg of 2-bromo-2-phenylsulfonylacetamide, and 100 g of polyvinyl butyral (10 wt.% ethyl alcohol solution).
  • composition (III) of Example 3 was coated on the polyester film, and dried to thereby obtain the film having thereon a layer containing therein a reducing agent.
  • the abovementioned heat-development type photosensitive raw material was left in a dark place for five weeks under conditions of 50° C. and a relative humidity (RH) of 80%. Thereafter, the photosensitive surface of this photosensitive raw material and the surface of the abovementioned polyester film where the composition (III) had been coated were sufficiently contacted, and then a pretreatment by heating was conducted for 3 seconds at 130° C. In continuation to this pretreatment, an image exposure was carried out for 15 seconds on this photosensitive material from the side of the polyester film through a positive image by the use of a tungsten lamp (2,500 lux), followed by the heat-development for four seconds at 130° C. by means of a roller type heating device. A visible negative print image could be obtained, which was made a specimen S-16.
  • RH relative humidity
  • the composition (III) was coated in advance on the photosensitive layer of the abovementioned photosensitive raw material, and dried sufficiently to prepare the heat-development type photosensitive material. Subsequently, this photosensitive material was left in a dark place for five weeks under conditions of 50° C. and a relative humidity (RH) of 80%, after which the pre-treatment under heat, image exposure, and heat-development were conducted in the same way as in preparing the specimen S-16, thereby obtaining a specimen S-17.
  • RH relative humidity
  • the specimen S-1 prepared in Example 1 above and having thereon a negative visible print image was used as an electrostatic printing master, and the following operations were conducted.
  • a corona discharge of +7 kV was uniformly imparted to the specimen S-1 as the electrostatic printing master, after which a negatively charged toner was developed by the magnet brush developing method, whereupon a positive toner image was obtained. Then, an image transfer paper was laid over this tone image, and the abovementioned corona discharge was imparted from the side of the image transfer paper, as the result of which a visible transfer image free from the ground fogging was clearly obtained on the transfer paper.
  • the silver image exhibited faithful reproducibility to the original image, there could be formed an electrostatic charge image in correspondence to the original image, hence the toner image was recognized to have been a very faithful photographic image corresponding to the original image.
  • Example 1 Accordingly, the heat-development type photosensitive raw material and the image forming method in Example 1 were recognized to provide a very excellent electrostatic printing master.
  • the specimens S-3, S-5, S-7, S-9, S-11, S-12, S-14, and S-16 were examined in the same way as in Example 12 above as to whether they had the performance suitable as the electrostatic printing master. Very favorable results as is the case with the specimen S-1 were obtained, and all of these specimens were recognized to have had the expected performance as the electrostatic printing master.
  • the specimen S-12 was subjected to the following operations with a view to examining whether it had the performance as the electrostatic printing master.
  • the thus prepared photosensitive sheet was left for two weeks in an environment of 50° C. and 80% RH, after which exposure was conducted on one portion of this photosensitive sheet for two seconds using a tungsten lamp of 60 lux as the light source.
  • This exposed photosensitive sheet was then subjected to the development under heat for two seconds by the use of a roller type heating device, whereupon the maximum photographic reflection density of the exposed portion was found to be 0.4 (the specimen S-18).
  • the photosensitive layer of this photosensitive sheet On the remaining portion of the photosensitive layer of this photosensitive sheet, there was further applied a solution (the composition V) composed of 1.5 g of 2,2'-methylenebis-6-t-butyl-p-cresol, 0.3 g of phthalazinone, and 15 g of acetone, which was soaked in a spronge. Then, the coated layer was dried under a natural condition. Subsequently, the exposure and the heat-development were conducted on this portion of the photosensitive sheet in the same manner as mentioned above. The maximum photographic reflection density at the exposed portion was found to be 1.5 (the specimen S-19).
  • the heat-development type photosensitive material coated with the abovementioned composition V was subjected to the image exposure for two seconds through a position image by the use of a tungsten lamp of 60 lux as the light source, and then subjected to the heat-development for two seconds at 130° C., thereby obtaining a negative print image. This was made the electrostatic printing master.
  • the thus obtained heat-development type photosensitive material (photosensitive sheet) was left for two weeks in an environment of 50° C. and 80% RH, after which an image-exposure was conducted for two seconds using a tungsten lamp of 60 lux as the light source.
  • composition XX a solution (composition XX) containing therein a development accelerator consisting of 1.5 g of 2,2'-methylenebis(6-t-butyl-p-cresol), 0.3 g of phthalazinone, and 15 g of acetone was soaked in a sponge roller, and then applied onto the surface of the abovementioned photosensitive material, followed by drying under a natural condition.
  • the photosensitive material was then subjected to the development under heat for two seconds at 130° C. by the use of a roller type heating device, whereupon the reflection density of the exposed portion thereof became 1.5.
  • the reflection density of the exposed portion was 0.35.
  • a sheet of benzotriazole silver was formed in the same manner as in Example 17, with the exception that benzotriazole silver was used in place of a mixture of silver behenate and behenic acid in equivalent mol ratio.
  • This photosensitive sheet was left for two weeks in a dark place in an environment of 50° C. and 80% RH, after which the same composition XX was coated thereon in the same manner as in Example 17. Then, a negative silver image was formed on this photosensitive sheet, followed by the electric charging, the development, the image-transfer, and the image fixation as in the case with Example 17, whereby a clear visible image free from the fogging was obtained.
  • the photosensitive sheet obtained in Example 15 was left for two weeks in an environment of 50° C. and 80% RH, after which it was subjected to an image exposure for two seconds by the use of a tungsten lamp of 60 lux as the exposure light source.
  • a sheet was prepared by coating a paper substrate with a solution composed of 0.3 g of hydroquinone, 0.3 g of phthalazinone, 10 g of acetone, and 5 g of ethyl cellulose (15% ethyl acetate solution) by means of a coating rod #24.
  • This coated sheet was overlaid at its coated surface on the abovementioned exposed photosensitive sheet, followed by heat treatment for two seconds at 130° C., whereupon the maximum photographic reflection density became 1.3.
  • the thus prepared sheets were left in a dark place for different time periods, respectively. That is, the sheet which was left in the dark place for a single day was designated as a sample S 1 -20, the sheet left for 30 days was designated as a sample S 30 -20, and the sheet left for 10 days in an environment of 50° C. and 80% RH was designated as S 10 -20.
  • These specimen sheets were then illuminated for 10 seconds with a tungsten lamp of 100W which was set 30 cm distant from the sheet, after which it was subjected to the development under heat by a roller type heat development device (at 130° C.).
  • the maximum density (D max ) and the fog density (D min ) the results as shown in Table 10 below were obtained. In other words, the developing property of the sheets became lowered with lapse of time.

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US3649280A (en) * 1968-11-29 1972-03-14 Eastman Kodak Co Photographic elements and compositions
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US8945686B2 (en) * 2007-05-24 2015-02-03 Ncc Method for reducing thin films on low temperature substrates
US20150176133A1 (en) * 2007-05-24 2015-06-25 Ncc Nano, Llc Method for Reducing Thin Films on Low Temperature Substrates
US9839139B2 (en) * 2007-05-24 2017-12-05 Ncc Nano, Llc Method for reducing thin films on low temperature substrates
US11172579B2 (en) * 2009-03-25 2021-11-09 Ncc Nano, Llc Method for reducing thin films on low temperature substrates

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